JPS62231014A - High-strength polymetaphenylene isophthalamide yarn and production thereof - Google Patents
High-strength polymetaphenylene isophthalamide yarn and production thereofInfo
- Publication number
- JPS62231014A JPS62231014A JP61293528A JP29352886A JPS62231014A JP S62231014 A JPS62231014 A JP S62231014A JP 61293528 A JP61293528 A JP 61293528A JP 29352886 A JP29352886 A JP 29352886A JP S62231014 A JPS62231014 A JP S62231014A
- Authority
- JP
- Japan
- Prior art keywords
- fibers
- fiber
- manufacturing
- organic solvent
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 polymetaphenylene isophthalamide Polymers 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 106
- 238000005406 washing Methods 0.000 claims abstract description 43
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- 239000003960 organic solvent Substances 0.000 claims abstract description 37
- 238000009987 spinning Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 35
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical compound NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000835 fiber Substances 0.000 claims description 145
- 239000002904 solvent Substances 0.000 claims description 28
- 239000013078 crystal Substances 0.000 claims description 19
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 16
- 238000002166 wet spinning Methods 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- LDYJXVUOVPVZKA-UHFFFAOYSA-N Methaphenilene Chemical compound C=1C=CC=CC=1N(CCN(C)C)CC1=CC=CS1 LDYJXVUOVPVZKA-UHFFFAOYSA-N 0.000 abstract 1
- 229950000498 methaphenilene Drugs 0.000 abstract 1
- 230000015271 coagulation Effects 0.000 description 12
- 238000005345 coagulation Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 6
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920006240 drawn fiber Polymers 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 210000003323 beak Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
- D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、従来のポリメタフェニレンイソフタラミド系
繊維に比べて著しく高い強度を有する新規なポリメタフ
ェニレンイソフタラミド系繊維、及び該ｍ維を工業的に
製造する新規な方法に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention provides a novel polymetaphenylene isophthalamide fiber that has significantly higher strength than conventional polymetaphenylene isophthalamide fibers, and This invention relates to a new method for industrially manufacturing fibers.
（従来技術）
例えば、米国特許第３，２８７，３２４号、同第３．３
００，４５０号、同第３，５６０，１３７＠及び同第４
．０７３，８３７号等に記載の如く、ポリメタフェニレ
ンイソフタラミド繊維は従来公知であり、「コーネック
ス」 （登録商標）、ｒＮＯＭＥＸＪ （登録商標）
などの商品名で市販されている。この繊維は、すぐれた
耐熱性と難燃性とを有するため、その特性を発揮し得る
産業用、衣料用の各分野の各分野に使用されている。(Prior art) For example, U.S. Patent No. 3,287,324, U.S. Patent No. 3.3
No. 00,450, No. 3,560,137 @ and No. 4
．． As described in No. 073,837, etc., polymetaphenylene isophthalamide fibers are conventionally known, such as "Conex" (registered trademark) and rNOMEXJ (registered trademark).
It is commercially available under product names such as. Since this fiber has excellent heat resistance and flame retardancy, it is used in various industrial and clothing fields where these characteristics can be exhibited.
しかしながら、従来のポリメタフエニレンイソフタラミ
ド繊維は、その機械的物性が未だ充分とは云えず、特に
破断時の強度が高々５．５ｇ／ｄｅ程度であるため、よ
り高い強度が要求される分野、例えば、ゴム補強材、樹
脂補強材、バッグフィルター用フェルトの基材、各種ベ
ルト等の分野への使用が制限されている。However, the mechanical properties of conventional polymetaphenylene isophthalamide fibers are still not sufficient, and in particular, the strength at break is only about 5.5 g/de, so higher strength is required. For example, use in the fields of rubber reinforcing materials, resin reinforcing materials, felt base materials for bag filters, various belts, etc. is restricted.
このため、高強力全芳香族ポリアミド繊維として、ポリ
パラフェニレンテレフタラミド４１１１ｉが製造されて
いるが、該繊維は製造コストが高いばかりでなく、破断
時の強度は２０ｇ／ｄａ以上と非常に大きいものの伸度
は約５％以下と小さいため、ある程度以上の伸度が要求
される分野には適さない。For this reason, polyparaphenylene terephthalamide 4111i is produced as a highly tenacious wholly aromatic polyamide fiber, but this fiber is not only expensive to manufacture, but also has a very high strength at break of 20 g/da or more. Since the elongation of the material is as small as about 5% or less, it is not suitable for fields that require elongation above a certain level.
また、該繊維は使用中にフィブリル化しやすいという欠
点もある。Another drawback is that the fibers tend to fibrillate during use.
（発明の目的）
本発明の第１の目的は、従来のポリメタフェニレンイソ
フタラミド繊維に比べて著しく高い強度とタフネス（即
ち、６．５ｇ／ｄａ以上の破断強度と３５以上のシルク
ファクター）を有する新規なポリメタフェニレンイソフ
タラミド系繊維を提供することにある。(Objective of the Invention) The first object of the present invention is to have significantly higher strength and toughness than conventional polymetaphenylene isophthalamide fibers (i.e., breaking strength of 6.5 g/da or more and silk factor of 35 or more). An object of the present invention is to provide a novel polymetaphenylene isophthalamide fiber having the following properties.
本発明の第２の目的は、上記の繊維を工業的に製造する
ための新規な方法を提供することにある。A second object of the present invention is to provide a new method for industrially producing the above-mentioned fibers.
（発明の構成）
上記の目的は、本発明に係る高強度ポリメタフェニレン
イソフタラミド系繊維及び上記繊Ｎ製造方法によって達
成される。(Structure of the Invention) The above object is achieved by the high-strength polymetaphenylene isophthalamide fiber and the method for producing fiber N according to the present invention.
即ち、本発明のポリメタフェニレンイソフタラミド系繊
維は、ポリマー繰返し単位の少くとも９５モル％がメタ
フェニレンイソフタラミドからなりカツポＩＪ Ｖ−１
１度０．５ｇ／ １００ｍの無水Ｎ−メチル−２−ピロ
リドン溶液にて３０℃の温度で測定した固有粘度［η］
ｒが０．５〜２．５であるポリメタフェニレンイソフタ
ラミド系重合体からなる繊維であって、０．１８〜０．
２２の複屈折率、４５〜５５％の結晶化度及び３５〜４
５人の結晶サイズを有し、かつ破断時の強度が６．５ｇ
／ｄｅ以上、シルクファクターが３５以上であることを
特徴とするものである。That is, the polymetaphenylene isophthalamide fiber of the present invention has at least 95 mol% of the polymer repeating units composed of metaphenylene isophthalamide,
Intrinsic viscosity [η] measured in an anhydrous N-methyl-2-pyrrolidone solution of 0.5 g/100 m at a temperature of 30°C
A fiber made of a polymetaphenylene isophthalamide polymer having an r of 0.5 to 2.5, the fiber having an r of 0.18 to 0.
Birefringence of 22, crystallinity of 45-55% and 35-4
It has a crystal size of 5 people and a strength at break of 6.5g.
/de or more, and the silk factor is 35 or more.
また、本発明のポリメタフェニレンイソフタラミド系繊
維の製造方法は、ポリマー繰返し単位の少くとも９５モ
ル％がメタフェニレンイソフタラミドからなりかつポリ
マー濃度０．５ｇ７１００Ｉｒｄｌの無水Ｎ−メチル−
２−ピロリドン溶液にて３０℃の温度で測定した固有粘
度［η］が０．７〜２．５であるポリメタフェニレンイ
ソフタラミド系重合体を、有線溶媒に溶解して紡糸ドー
プとなし、該紡糸ドープを紡糸して得た未延伸繊維を、
（イ）第１次水洗工程に試して繊維中の有機溶媒含有率
を１５〜３０重堡％に調整し、（○）次いで第１次水浴
延伸工程に賦して繊維中の有様溶媒含有率が１５〜３０
重量％の状態において少くとも１段で１．１〜１．５倍
に延伸し、（ハ）引続き第２次水洗工程に試して繊維中
の有機溶媒含有率を１５重量％未満に調整した後、（−
４第２次水浴延伸工程に賦して少くとも１段にて １．
１倍以上に延伸し、（ホ）次いで乾燥し、（へ）しかる
後乾熱延伸工程に試して全延伸倍率が４．０〜７．０倍
となる倍率で延伸することを特徴とする方法である。Further, the method for producing the polymetaphenylene isophthalamide fiber of the present invention includes anhydrous N-methyl-
A polymetaphenylene isophthalamide polymer having an intrinsic viscosity [η] of 0.7 to 2.5 measured in a 2-pyrrolidone solution at a temperature of 30° C. is dissolved in a wired solvent to prepare a spinning dope; The undrawn fiber obtained by spinning the spinning dope,
(b) Adjust the organic solvent content in the fiber to 15 to 30% by weight in the first water washing process, (○) Then add it to the first water bath drawing process to contain the specific solvent in the fiber. Rate is 15-30
After stretching the fiber by a factor of 1.1 to 1.5 in at least one stage in a state of % by weight, and (c) subsequently performing a second water washing step to adjust the organic solvent content in the fiber to less than 15% by weight. , (−
4 Added to the second water bath stretching process in at least one stage 1.
A method characterized by stretching the material by a factor of 1 or more, (e) then drying, and (e) then performing a dry heat stretching step to obtain a total stretching ratio of 4.0 to 7.0 times. It is.
本発明の高強力ポリメタフェニレンイソフタラミド系繊
維は、ポリマー繰返し単位の９５モル％以上がメタフェ
ニレンイソフタラミド単位からなりかつその固有粘度［
η］ｆが０．７〜２．５という特定範囲内にあるポリメ
タフェニレンイソフタラミド系重合体によって構成され
る。そして、従来のポリメタフェニレンイソフタラミド
繊維に比して格段に大きな分子配向、即ち複屈折率にし
て０．１８〜０．２２という分子配向を有し、また結晶
化度も大ぎくＸ線法で求められる結晶化度にして４５〜
５５％の範囲内にある。その反面、従来のポリメタフェ
ニレンイソフタラミド繊維に比して小さな結晶サイズを
有し、Ｘ線回折から求められる結晶サイズが３５〜４５
人の範囲内にある。The high-strength polymetaphenylene isophthalamide fiber of the present invention is characterized in that 95 mol% or more of the polymer repeating units are metaphenylene isophthalamide units, and its intrinsic viscosity [
[eta]]f is within a specific range of 0.7 to 2.5. It has a much larger molecular orientation than conventional polymetaphenylene isophthalamide fibers, that is, a molecular orientation with a birefringence of 0.18 to 0.22, and also has a high degree of crystallinity. The crystallinity required by the method is 45~
It is within the range of 55%. On the other hand, it has a smaller crystal size compared to conventional polymetaphenylene isophthalamide fibers, and the crystal size determined from X-ray diffraction is 35 to 45.
within the range of humans.
本発明のポリメタフェニレンイソフタラミド系ｔｌ維を
構成するポリマーは、ポリメタフェニレンイソフタラミ
ド単独重合体であることが好ましいが、ポリマー繰返し
単位の９５モル％以上、好ましくは９８モル％以上がメ
タフェニレンイソフタラミドである重合体であればよく
、５モル％以下、好ましくは２モル％以下の第３成分を
共重合したものでもよい。The polymer constituting the polymetaphenylene isophthalamide-based TL fiber of the present invention is preferably a polymetaphenylene isophthalamide homopolymer, and 95 mol% or more, preferably 98 mol% or more of the polymer repeating units are Any polymer may be used as long as it is metaphenylene isophthalamide, and it may be copolymerized with 5 mol % or less, preferably 2 mol % or less of the third component.
第３成分が５モル％を超えると、繊維の結晶化度が低下
し、破断強度やタフネス等の物性も悪化する。If the content of the third component exceeds 5 mol %, the crystallinity of the fiber will decrease, and physical properties such as breaking strength and toughness will also deteriorate.
５モル％以下の割合で共重合し得る第３成分としては、
例えばテレフタル酸、バラフェニレンジアミン、メタキ
シリレンジアミン等があげられる。As the third component that can be copolymerized at a ratio of 5 mol% or less,
Examples include terephthalic acid, paraphenylene diamine, metaxylylene diamine, and the like.
繊維を構成するポリメタフェニレンイソフタラミド系重
合体の重合度は、該重合体を脱水したＮ−″メチルー２
−ピロリドンにポリマー濃度０．５ｇ／ １００ｍとな
るように溶解し３０℃で測定した固有粘度［η］ｆにし
て、０．１〜２．５、好ましくは１．２〜２．０の範囲
内にある。［η］［が０．７未満では、繊維の分子配向
度２結晶化度、結晶サイズ等を前述のように調整しても
、破断強度及びタフネスの大きなｍＭｌとはならず、本
発明の目的を達成し得ない。一方、重合体の固有粘度［
η］が２．５を超えるものは、紡糸ドープの粘度が異常
に高くなり、紡糸ドープの粘度を紡糸可能な粘度の限界
内に抑えようとすると紡糸ドープのポリマー濃度を極端
に小さくしなければならず良好な生産性にて紡糸するこ
とが不可能である。The degree of polymerization of the polymetaphenylene isophthalamide-based polymer constituting the fiber is determined by
- Intrinsic viscosity [η] f measured at 30°C after dissolving the polymer in pyrrolidone at a concentration of 0.5 g/100 m is within the range of 0.1 to 2.5, preferably 1.2 to 2.0. It is in. If [η][ is less than 0.7, even if the molecular orientation, crystallinity, crystal size, etc. of the fiber are adjusted as described above, the breaking strength and toughness will not be large, and the object of the present invention will not be achieved. cannot be achieved. On the other hand, the intrinsic viscosity of the polymer [
If η] exceeds 2.5, the viscosity of the spinning dope becomes abnormally high, and in order to keep the viscosity of the spinning dope within the viscosity limit that allows spinning, the polymer concentration in the spinning dope must be extremely reduced. Therefore, it is impossible to perform spinning with good productivity.
繊維を構成する上記重合体には、必要に応じ、着色剤、
紫外線吸収剤、耐光性安定剤、ｔｉ燃剤等の各種添加剤
を含有してもよい。The above-mentioned polymer constituting the fiber may contain a coloring agent, if necessary.
It may contain various additives such as ultraviolet absorbers, light resistance stabilizers, and Ti refueling agents.
本発明のポリメタフェニレンイソフタラミド系繊維は、
０．１８〜０．２２好ましくは０．１９〜０．２１の複
屈折率を有し、このことは該繊維が非常にへ度の分子配
向を有することを示す。また、該繊維は従来のポリメタ
フェニレンイソフタラミド繊維に比べて顕著に高い結晶
化度即ち４５〜５５％好ましくは４８〜５３％の結晶化
度を有し、ざらに、従来のポリメタフェニレンイソフタ
ラミド繊維に比べて小さい結晶サイズ、即ち３５〜４５
人、好ましくは３８〜４３人の結晶サイズを有する。The polymetaphenylene isophthalamide fiber of the present invention is
It has a birefringence of 0.18 to 0.22, preferably 0.19 to 0.21, indicating that the fiber has a highly helical molecular orientation. The fibers also have a significantly higher crystallinity, i.e. 45-55%, preferably 48-53%, than conventional polymetaphenylene isophthalamide fibers; Small crystal size compared to isophthalamide fibers, i.e. 35-45
have a crystal size of 38 to 43 people, preferably 38 to 43 people.
複屈折率が０．１８未満では、ＩＩＭの結晶化度が４８
％以上となり得ず、所望の破断強度、タフネス等を有す
るものとはならない。一方、複屈折率が０．２２を超え
ると、結晶化度が５５％より大となり、繊維の伸度が低
くなり繊維がもろくなる。また、結晶化度が４５％より
小さいと繊維は十分な強度を発現せず、逆に結晶化度が
５５％を超えるとｌＩＨの伸度が低くなりもろいｍ紺と
なる。When the birefringence is less than 0.18, the crystallinity of IIM is 48
% or more, and the desired breaking strength, toughness, etc. cannot be achieved. On the other hand, if the birefringence exceeds 0.22, the crystallinity will be greater than 55%, the elongation of the fiber will be low, and the fiber will become brittle. Furthermore, if the crystallinity is less than 45%, the fiber will not exhibit sufficient strength, and if the crystallinity exceeds 55%, the elongation of lIH will be low, resulting in a brittle dark blue color.
さらに、結晶サイズが３５人より小さいと、繊維におけ
る結晶部と非晶部との区分が不明確となり繊維の寸法安
定性が悪くなり、結晶サイズが４５人より大きいと、ｌ
ｌ維内部において結晶が１ｉＩｆ軸の方向に揃い難くな
り、繊維物性が低下する。Furthermore, if the crystal size is smaller than 35 particles, the division between the crystalline part and the amorphous part in the fiber becomes unclear, resulting in poor dimensional stability of the fiber, and if the crystal size is larger than 45 particles, the l
It becomes difficult for the crystals to align in the direction of the 1iIf axis inside the 1 fiber, and the physical properties of the fiber deteriorate.
本発明のポリメタフェニレンイソフタラミド系繊維にお
いて、このように高配向高結晶性にするとともに個々の
結晶の大きさを小さく制御することによって、該繊維の
もつ伸度を損うことなく、破断時の強度が従来のポリメ
タフェニレンイソフタラミド繊維に比べて約２０％以上
も向上し、かつシルクファクターで表わされるタフネス
も増大することは、全く予期し得ないことである。By making the polymetaphenylene isophthalamide fiber of the present invention highly oriented, highly crystalline, and controlling the size of individual crystals to be small, it is possible to break the fiber without impairing its elongation. It is completely unexpected that the strength of the fibers is improved by about 20% or more compared to conventional polymetaphenylene isophthalamide fibers, and the toughness expressed by the silk factor is also increased.
なお、本発明者らの研究によれば、本発明のポリメタフ
ェニレンイソフタラミド系繊維は、通常、９０〜９５％
の結晶配向度を有し、結晶配向度も従来の繊維に比べて
かなり高くなることが判明した。According to the research conducted by the present inventors, the polymetaphenylene isophthalamide fiber of the present invention usually has a content of 90 to 95%.
It was found that the degree of crystal orientation was considerably higher than that of conventional fibers.
また、本発明のポリメタフェニレンイソフタラミド系繊
維の形態はマルチフィラメント、ステーアルファイバー
の何れでもよく、繊度や断面形状も限定されないが、フ
ィラメント当りの繊度は一般に １〜１０ｄｅの範囲が
適当であり、断面形状は、円形、だ円形、三角形、まゆ
形その他任意の形状をとることができる。Further, the form of the polymetaphenylene isophthalamide fiber of the present invention may be either multifilament or stal fiber, and the fineness and cross-sectional shape are not limited, but the fineness per filament is generally in the range of 1 to 10 de. The cross-sectional shape can be circular, oval, triangular, eyebrow-shaped, or any other arbitrary shape.
゛上述の如き特定の微細構造に起因して、本発明のポリ
メタフェニレンイソフタラミド系繊維は、６．５ｇ／ｄ
ｅ以上、好ましくは７．０〜８．５ｇ／ｄｅの高い破断
強度を有する。そして、このような高い破断強度を有す
るにもかかわらず、本発明の繊維は破断時の伸度が２０
〜３０％という好適な値を有する。このため繊維が破断
に至るまでの仕事岱の目安となるシルクファクターは３
５以上となり、大きなタフネスを示す。゛Due to the specific microstructure as described above, the polymetaphenylene isophthalamide fiber of the present invention has a
It has a high breaking strength of 7.0 to 8.5 g/de, preferably 7.0 to 8.5 g/de. Despite having such a high breaking strength, the fiber of the present invention has an elongation of 20 at break.
It has a preferred value of ~30%. Therefore, the silk factor, which is a guideline for the amount of work it takes for the fiber to break, is 3.
5 or higher, indicating great toughness.
しかも、本発明のｔａｔａは、耐フィブリル性にもすぐ
れており、ポリパラフェニレンテレフタラミド繊維のよ
うに、使用中に繊維がフィブリル化するという問題はな
い。また、耐熱性も良好であり、３００℃における収縮
率が７％以下であり、熱に対する寸法安定性にもすぐれ
ている。Furthermore, the tata of the present invention has excellent fibril resistance, and unlike polyparaphenylene terephthalamide fibers, there is no problem of the fibers becoming fibrillated during use. It also has good heat resistance, with a shrinkage rate of 7% or less at 300°C, and excellent dimensional stability against heat.
なお、本発明の繊維において、ポリマーの全末端の２０
％以上がアニリン等の一官能性化合物によって封鎖した
ポリメタフェニレンイソフタラミド系重合体からなる繊
維は特に高温時に長時間保持した場合の強度維持率もす
ぐれたものとなる。In addition, in the fiber of the present invention, 20 at all ends of the polymer
Fibers made of polymetaphenylene isophthalamide polymers in which % or more of the fibers are blocked by monofunctional compounds such as aniline have excellent strength retention especially when held at high temperatures for long periods of time.
上述のような本発明の高強力ポリメタフェニレンイソフ
タラミド系繊維は、以下に述べる一連の工程からなる本
発明の方法により工業的に製造することができる。The high-strength polymetaphenylene isophthalamide fiber of the present invention as described above can be industrially produced by the method of the present invention comprising a series of steps described below.
即ら、まず、紡糸工程において、ポリマー繰返し単位の
９５モル％以上がメタフェニルイソフタラミドでありか
つ固有粘度［η］が０．７〜２．５、好ましくは１．２
〜２．０のポリメタフェニレンイソフタラミド系重合体
を有機溶媒に溶解した紡糸ドープを、少くとも１個の紡
糸孔を有する紡糸口金から押出し凝固浴中にて凝固させ
未延伸ｍ雑を形成する。この場合、紡糸ドープを直接凝
固浴中に押出してもよく、−たん空気中に押出した後直
ちに凝固浴中へ導入させて凝固させてもよい。一般に紡
糸ドープ中に塩化カルシウム、塩化リチウム等の無機塩
を添加すると？８ｗｌ−力が増大するため好ましいと云
われているが、本発明の方法では、実質的にかかる無機
塩を含まない方が好ましい。紡糸ドープ中に無機塩を含
むと、紡糸後に繊維中に含まれる無機塩を洗浄除去する
操作が煩雑で、繊維の製造工程が長くかつ複雑となる。That is, first, in the spinning step, 95 mol% or more of the polymer repeating units are metaphenylisophthalamide and the intrinsic viscosity [η] is 0.7 to 2.5, preferably 1.2.
A spinning dope in which a polymetaphenylene isophthalamide-based polymer of ~2.0 is dissolved in an organic solvent is extruded from a spinneret having at least one spinning hole and coagulated in a coagulation bath to form an unstretched material. do. In this case, the spinning dope may be directly extruded into the coagulation bath, or it may be extruded into air and immediately introduced into the coagulation bath to be coagulated. Generally speaking, what happens when inorganic salts such as calcium chloride and lithium chloride are added to the spinning dope? Although it is said to be preferable because it increases the 8wl-force, in the method of the present invention, it is preferable that the inorganic salt is substantially free of such an inorganic salt. If the spinning dope contains an inorganic salt, the operation of washing and removing the inorganic salt contained in the fiber after spinning is complicated, and the fiber manufacturing process becomes long and complicated.
紡糸ドープ調製のために使用する有様溶媒としては、極
性アミド系溶媒が適当であり、なかでもＮ−メチル−２
−ピロリドン、Ｎ、Ｎ’ −ジメチルホルムアミド又は
Ｎ、Ｎ’ −ジメタルアセトアミドが好ましい。紡糸ド
ープ中のポリマー濃度は、ポリマーの固有粘度によって
も異るが一般に１５〜３０重Ｇ％が好適である。As the specific solvent used for preparing the spinning dope, polar amide solvents are suitable, especially N-methyl-2
-pyrrolidone, N,N'-dimethylformamide or N,N'-dimetalacetamide are preferred. The concentration of the polymer in the spinning dope varies depending on the intrinsic viscosity of the polymer, but is generally 15 to 30% by weight G%.
一方、凝固浴は、塩化カルシウム、塩化マグネシウム、
塩化亜鉛などの無機塩の水溶液が用いられる。凝固浴の
温度は６０〜１００℃が好ましい。具体的な紡糸条件は
、例えば特公昭４８−１７５５１号、米国特許第４，０
７３，８３７号等に詳しく記載されている。On the other hand, the coagulation bath contains calcium chloride, magnesium chloride,
Aqueous solutions of inorganic salts such as zinc chloride are used. The temperature of the coagulation bath is preferably 60 to 100°C. Specific spinning conditions are described, for example, in Japanese Patent Publication No. 48-17551 and U.S. Patent No. 4.0.
It is described in detail in No. 73,837, etc.
凝固浴から引出された未延伸繊維は、次に、第１次水洗
工程において、繊維中に含まれる有機溶媒の一部を除去
し、繊維中の溶媒含有率を１５〜３０重量％に調整する
。なお、本発明でいう繊維中の溶媒含有率とは、溶媒を
全く含まない繊維の重量に対するｍ雑巾の有様溶媒の重
量を百分率で表わした値である。The undrawn fibers pulled out from the coagulation bath are then subjected to a first water washing step in which part of the organic solvent contained in the fibers is removed and the solvent content in the fibers is adjusted to 15 to 30% by weight. . In addition, the solvent content in the fibers as used in the present invention is a value expressed as a percentage of the weight of the solvent in the m rag to the weight of the fibers that do not contain any solvent.
この第１次水洗工程は、１個の水洗浴を使用して１段で
実施してもよく、２個以上の水洗浴を使用して２段以上
で実施してもよい。第１次水洗工程では、水洗浴中に紡
糸ドープ中の有機溶媒と同じ有様溶媒を１０〜４０重羽
％含むのが好ましく、また、第１次水洗工程における水
洗浴の温度は２０〜７０℃が好ましい。This first water washing step may be carried out in one stage using one washing bath, or may be carried out in two or more stages using two or more washing baths. In the first water washing step, it is preferable that the water washing bath contains 10 to 40% of the same specific solvent as the organic solvent in the spinning dope, and the temperature of the water washing bath in the first water washing step is 20 to 70%. °C is preferred.
上述の第１次水洗工程において有機溶媒含有率を調整さ
れたｍ雑は、次に、第１次水浴延伸工程において１．１
〜１．５倍の全延伸倍率に延伸される。The m miscellaneous material whose organic solvent content was adjusted in the first water washing step described above is then reduced to 1.1 in the first water bath stretching step.
Stretched to a total stretch ratio of ~1.5 times.
この第１次水浴延伸は１段で行ってもよく、２段以上に
分けて行ってもよい。殆どの場合、この第１次水浴延伸
工程でも繊維中の有機溶媒の一部が除去されるが、延伸
中に有機溶媒含有率が１５重量％未満に低下しないよう
延伸浴組成を調整する必要がある。このため、延伸浴中
にドープ中の有機溶媒と同じ有機溶媒を３〜３０重量％
含むのが好ましい。また、延伸浴温度は５０〜９５℃、
好ましくは６０〜９０℃とするのが適当である。This primary water bath stretching may be performed in one stage, or may be performed in two or more stages. In most cases, this first water bath drawing step also removes some of the organic solvent in the fiber, but it is necessary to adjust the drawing bath composition so that the organic solvent content does not fall below 15% by weight during drawing. be. For this reason, 3 to 30% by weight of the same organic solvent as the organic solvent in the dope is added to the stretching bath.
It is preferable to include. In addition, the stretching bath temperature is 50 to 95°C,
The temperature is preferably 60 to 90°C.
なお、第１次水浴延伸における延伸倍率は１．１〜１．
５倍とする（２段以上に分けて延伸する場合は全延伸倍
率にして １．１〜１．５倍とする）必要があり、この
延伸倍率が１．１倍未満では、この延伸工程の効果が乏
しく、最終的に得られる延伸繊維の結晶構造１分子配向
が不十分となり、所望の強度、タフネスを有する繊維と
はなり得ない。また、延伸倍率が１．５倍を超えると、
第１次水浴延伸工程で分子の流れ（フロー）が優先し配
向度の上らない繊維となるため、この延伸工程の効果が
乏しい。Note that the stretching ratio in the first water bath stretching is 1.1 to 1.
5 times (if stretching is carried out in two or more stages, the total stretching ratio should be 1.1 to 1.5 times), and if this stretching ratio is less than 1.1 times, the stretching process is The effect is poor, and the crystal structure of the ultimately obtained drawn fibers is insufficiently oriented per molecule, making it impossible to obtain fibers with desired strength and toughness. In addition, when the stretching ratio exceeds 1.5 times,
In the first water bath drawing step, molecular flow takes precedence, resulting in fibers with poor orientation, so the effect of this drawing step is poor.
好適な第１次水浴延伸工程では、第１次水洗工程を経た
４１維は、先ずドープ中の有機溶媒と同じ有機溶媒を１
０〜３０重ａ％の濃度で含む第１浴（水浴）において５
０〜７０℃の温度で１．１〜１．４倍に延伸され、引続
き上記有□溶媒を５〜１５重口％であってかつ第１浴よ
りも低い濃度で含む第２浴（水浴）において７０〜９０
℃の温度で第１次水浴延伸工程における全延伸倍率が１
．１〜１．５倍となるように延伸される。このような延
伸条件を採用すると、第１次水浴延伸がきわめて円滑に
実施され、しかも、最終的に得られる延伸繊維の物性が
特にすぐれたものとなるので好ましい。In the preferred first water bath stretching step, the 41 fibers that have undergone the first water washing step are first treated with one portion of the same organic solvent as that in the dope.
In the first bath (water bath) containing at a concentration of 0 to 30% by weight, 5
A second bath (water bath) that is stretched 1.1 to 1.4 times at a temperature of 0 to 70°C and subsequently contains the above-mentioned solvent at a concentration of 5 to 15% by weight and lower than that of the first bath. 70-90 in
The total stretching ratio in the first water bath stretching step is 1 at a temperature of ℃.
．． It is stretched 1 to 1.5 times. It is preferable to employ such drawing conditions because the primary water bath drawing can be carried out very smoothly and the finally obtained drawn fibers will have particularly excellent physical properties.
第１次水浴延伸工程を経た繊維は、次に、第２次水洗工
程に送られ、ここで繊維中の有機溶媒含有率を１５重量
％未満に低減させる。この第２次水洗工程も１段又は２
段以上で実施することができる。The fibers that have undergone the first water bath drawing step are then sent to a second water washing step, where the organic solvent content in the fibers is reduced to less than 15% by weight. This second water washing process can also be carried out in one or two stages.
It can be carried out in stages or more.
第２次水洗工程後の繊維中の有機溶媒含有率が１５重量
％以上であると、後続の第２次水浴延伸工程で繊維の分
子配向が上らず、さらに次の乾熱延伸での結晶化が進ま
ないため、所望の物性を有する４ＨＮが得られない。If the organic solvent content in the fiber after the second water washing step is 15% by weight or more, the molecular orientation of the fiber will not improve in the subsequent second water bath drawing step, and crystallization will occur in the next dry heat drawing. Since the conversion does not proceed, 4HN having desired physical properties cannot be obtained.
第２次水洗工程は、１浴又は２浴以上の水洗浴を用いて
実施されるが、水洗浴としては水のみ、またはドープ中
の有機溶媒と同じ有機溶媒を１０重量％以下の濃度で含
む水からなる浴が用いられる。The secondary water washing step is carried out using one or more washing baths, and the washing bath contains only water or the same organic solvent as the organic solvent in the dope at a concentration of 10% by weight or less. A bath consisting of water is used.
水洗浴の温度は６０〜９０℃が好ましい。The temperature of the water washing bath is preferably 60 to 90°C.
第２次水洗工程で有機溶媒含有率を１５重通％未満に調
整された繊維は、引続き第２次水浴延伸工程において、
１．１倍以上、好ましくは１．５〜３．０倍に少くとも
１個の延伸浴を用い少くとも１段で延伸される。第２次
水浴延伸工程でも延伸中に繊維内に残留する有機溶媒の
一部または全部が除去される。延伸浴としては水のみ又
はドープ中の有機溶媒と同じ有機溶媒を１０重通％未満
の濃度で含む水が用いられる。延伸浴温度は９０〜１０
０℃が好ましい。The fibers whose organic solvent content was adjusted to less than 15% by weight in the second water washing step are then subjected to the second water bath stretching step.
It is stretched by at least 1.1 times, preferably 1.5 to 3.0 times, in at least one stage using at least one stretching bath. In the second water bath drawing step, part or all of the organic solvent remaining in the fibers during drawing is removed. As the stretching bath, water alone or water containing the same organic solvent as the organic solvent in the dope at a concentration of less than 10% by weight is used. Stretching bath temperature is 90-10
0°C is preferred.
第２次水浴延伸の後に、更に、水のみでｍＮを水洗して
残留溶媒を完全に除去するのが好ましい。After the second water bath stretching, it is preferable to further wash mN with only water to completely remove the residual solvent.
かくして第２次水浴延伸を行ない、更に必要に応じて水
洗を施した繊維は、例えば１００〜１４０℃の乾燥ロー
ラに数回巻回して乾燥した後、乾熱延伸を行う。The fibers thus subjected to the second water bath drawing and further washed with water if necessary are wound around a drying roller several times at, for example, 100 to 140°C, dried, and then subjected to dry heat drawing.
乾熱延伸工程では、繊維は、熱板又は加熱室中で、紡糸
後の全延伸倍率が４．０〜７．０倍、好ましくは４．５
〜６．５倍となるように延伸される。延伸温度は３００
〜４５０℃が好ましく、この乾熱延伸工程での延伸倍率
は１．５〜２．５倍が適当である。In the dry heat drawing process, the fibers are drawn on a hot plate or in a heating chamber at a total draw ratio of 4.0 to 7.0 times, preferably 4.5 times after spinning.
It is stretched to 6.5 times. Stretching temperature is 300
-450 degreeC is preferable, and the draw ratio in this dry heat drawing process is suitably 1.5-2.5 times.
なお、全延伸倍率が４．０倍よりも低いと、得られる繊
維の破断強度が６．５ｇ／ｄｅより低くなり、また、７
．０倍より高いと、延伸中に毛羽や断糸が発生するので
好ましくない。In addition, if the total stretching ratio is lower than 4.0 times, the breaking strength of the obtained fiber will be lower than 6.5 g/de, and
．． If it is higher than 0 times, fluff and yarn breakage will occur during stretching, which is not preferable.
上述の如く紡糸直後の繊維にそれぞれ特定条件で第１次
水洗工程−第１次水浴延伸工程−第２次水洗工程−第２
次水浴延伸工程＋最終水洗工程÷乾燥工程−乾熱延伸工
程を連続的又はバッチ式に実施し、ざらに必要に応じて
熱処理、捲縮加工。As mentioned above, the fibers immediately after spinning are subjected to a first water washing process, a first water bath drawing process, a second water washing process, and a second water washing process under specific conditions.
The next water bath stretching process + final water washing process ÷ drying process - dry heat stretching process is carried out continuously or batchwise, and the roughness is heat treated and crimped as necessary.
その他の仕上げ加工を行うことにより、良好な生産性に
て本発明の高強力ポリメタフェニレンイソフタラミド系
繊維を製造することができる。By performing other finishing processes, the high-strength polymetaphenylene isophthalamide fiber of the present invention can be produced with good productivity.
（発明の効果）
上述の如き本発明のポリメタフェニレンイソフタラミド
系繊維は、従来のポリメタフェニレンイソフタラミド繊
維に比べて約２０％以上も強度が大きく、しかも十分な
伸度を有し、さらに耐熱性にも優れているため、従来ポ
リメタフェニレンイソフタラミド系繊維が使用できなか
ったゴム補強材。(Effects of the Invention) The polymetaphenylene isophthalamide fiber of the present invention as described above has a strength approximately 20% higher than that of conventional polymetaphenylene isophthalamide fibers, and also has sufficient elongation. Furthermore, due to its excellent heat resistance, polymetaphenylene isophthalamide fibers cannot be used as rubber reinforcing materials.
樹脂補強材、バッグフィルター用フェルトの基材等の分
野にも使用が可能となり、また、従来のポリメタフェニ
レンイソフタラミド繊維が使用されていた分野でも同程
度の強度の製品を製造するために必要とする繊維の使用
量を減らすことができるので、製品の軽ｌ化、短小化等
をはかることができる。It can now be used in fields such as resin reinforcement materials and felt base materials for bag filters, and can also be used to manufacture products with similar strength in fields where conventional polymetaphenylene isophthalamide fibers were used. Since the amount of fiber required can be reduced, products can be made lighter and shorter.
さらに、本発明のポリメタフェニレンイソフタラミド系
繊維は、初期強度が高い上に、高温での強度保持率は従
来のポリメタフェニレンイソフタラミド繊維と同等であ
るため、バッグフィルター等の高温で常時使用される製
品に使用したときには、製品の寿命が延長するという効
果も存する。Furthermore, the polymetaphenylene isophthalamide fiber of the present invention not only has high initial strength, but also has the same strength retention rate at high temperatures as conventional polymetaphenylene isophthalamide fiber, so it can be used in high-temperature applications such as bag filters. When used in products that are constantly used, it also has the effect of extending the life of the product.
また、本発明の製造方法によれば、上述の高強度ポリメ
タフェニレンイソフタラミド系繊維を安定した工程調子
で効率的に製造することができる。Further, according to the manufacturing method of the present invention, the above-mentioned high-strength polymetaphenylene isophthalamide fiber can be efficiently manufactured in a stable process condition.
（各指標の測定法） 次に、本発明でいう各指標の測定法を説明する。(Measurement method of each index) Next, a method for measuring each index in the present invention will be explained.
（Ｊ 固有粘度（［η］、［ηＥｆ＞
固有粘度はポリマーの分子量を表わす目安となるもので
、本発明では、無水Ｎ−メチル−２−ピロリドン１００
ｄにポリマー又は繊維０．５ｇを溶解した溶液の３０℃
における固有粘度で表わす。(J Intrinsic viscosity ([η], [ηEf>
A solution of 0.5 g of polymer or fiber dissolved in d at 30°C
It is expressed as the intrinsic viscosity at .
なお、ここでは原料ポリマーの固有粘度を［η］、繊維
とした後の固有粘度を［η］［とする。Note that here, the intrinsic viscosity of the raw material polymer is [η], and the intrinsic viscosity after being made into fibers is [η][.
（ｂ〉 結晶化度
通常のＸ線測定法による。但し、結晶部、非晶部の算出
は、以下の通りとする。(b) Crystallinity According to the usual X-ray measurement method. However, the calculation of crystalline parts and amorphous parts is as follows.
（１）２θの範囲は、１２°から３２″までとする。(1) The range of 2θ is from 12° to 32″.
（籠） 非晶部２θ＝１７°から２θ＝３０°まで直
線を引き、この線分と２θ＜１７” 、 ２θ＞ ３０
”の子午回折曲線とからなる曲線を非晶散乱曲線とし、
これと無配向近似曲線との間の部分（Ｃ）が結晶の寄与
、これと空気散乱曲線との間の部分（Ａ）が非晶の寄与
とする。(Cage) Draw a straight line from the amorphous part 2θ=17° to 2θ=30°, and connect this line segment with 2θ<17”, 2θ>30
The curve consisting of the meridional diffraction curve of " is the amorphous scattering curve,
The portion (C) between this and the non-oriented approximate curve is the contribution of crystals, and the portion (A) between this and the air scattering curve is the contribution of amorphous.
結晶化度＝Ｃ／Ｔ （１−１２，７／ １００）但し、
Ｔ＝△＋Ｃ
＜Ｃ） 結晶サイズ
特公昭５９−１４５６７号公報第１９〜２２欄又は特公
昭６１−３８８６号公報第１２〜１３欄に記載の方法に
よる。Crystallinity = C/T (1-12,7/100) However,
T=Δ+C<C) Crystal size According to the method described in Japanese Patent Publication No. 14567/1988, columns 19 to 22 or columns 12 to 13 of Japanese Patent Publication No. 3886/1986.
（小 結晶配向度
例えば特公昭６１−３８８６号公報第１３〜１４欄に記
載の如き通常の簡便法による。(Small degree of crystal orientation. For example, by a conventional and convenient method as described in columns 13 to 14 of Japanese Patent Publication No. 61-3886.
なお、ポリメタフェニレンイソフタラミドでは、２θ＝
２７．３° （１１０）反射が赤道上の最強ピークで
あるのでこれを用いる。In addition, in polymetaphenylene isophthalamide, 2θ=
The 27.3° (110) reflection is used because it is the strongest peak on the equator.
配向角＝ （１８０’ −Ｈ” ／ １８０°）ｘｌｏ
ｏ（％）但し、Ｈは半価幅
（ｅ） 破断時の強度、伸度
ＪＩＳ Ｌ−１０１５（１９８３）の「化学繊維ステ
ーブルの試験方法」による。Orientation angle = (180' - H" / 180°)xlo
o (%) However, H is half width (e) Strength and elongation at break According to "Testing method for chemical fiber stable" of JIS L-1015 (1983).
（ｆ） シルクファクター 次式により算出する。(f) Silk factor Calculated using the following formula.
シルクファクター
＝強度（ｚ／ｄｅ）ｘＪ順［（％）
（う） 繊維中の有機溶媒含有率
特公昭５３−１０１１３号公報第４欄に記載の残留溶媒
量Ｓの測定法による。Silk factor = strength (z/de) x J order [(%) (c) Organic solvent content in fibers According to the method for measuring the amount of residual solvent S described in column 4 of Japanese Patent Publication No. 10113/1983.
〈ｈ） 水洗浴、延伸浴中の有機溶媒濃度次式により
算出する。<h) Concentration of organic solvent in washing bath and stretching bath Calculated using the following formula.
有機溶媒濃度＝（浴中有機溶媒の重量／浴の全重量）ｘ
１００％
（実施例）
次に本発明の実施例及び比較例を詳述するが、本発明は
これらにより何ら限定されるものではない。Organic solvent concentration = (weight of organic solvent in bath/total weight of bath) x
100% (Example) Next, Examples and Comparative Examples of the present invention will be described in detail, but the present invention is not limited thereto.
実施例１
特開昭４７−１０８６３号公報に記載の界面重合法によ
り製造された固有粘度［η］ １．４５のポリメタフ
ェニレンイソフタラミドｍ合体をＮ−メチル−２−ピロ
リドンからなる溶媒に２０．５ｆｆｉ ｍ％の濃度で溶
解して紡糸ドープを調製し、この紡糸ドープを用いて特
公昭４８−１７５５１号公報に記載の湿式紡糸法に従っ
て、孔径０．０７ Ｍの紡糸孔を１００００個設けた紡
糸口金から塩化カルシウム濃度４５％、温度９０℃の塩
化カルシウム水溶液からなる凝固浴中に紡糸した。。Example 1 A polymetaphenylene isophthalamide m polymer having an intrinsic viscosity [η] of 1.45 produced by the interfacial polymerization method described in JP-A-47-10863 was dissolved in a solvent consisting of N-methyl-2-pyrrolidone. A spinning dope was prepared by dissolving it at a concentration of 20.5ffi m%, and using this spinning dope, 10,000 spinning holes with a pore diameter of 0.07 M were formed according to the wet spinning method described in Japanese Patent Publication No. 17551/1983. The fibers were spun from a spinneret into a coagulation bath consisting of an aqueous calcium chloride solution with a calcium chloride concentration of 45% and a temperature of 90°C. .
凝固した未延伸繊維は、凝固浴から引出された段階で４
５重量％の溶媒を含んでいた。The coagulated undrawn fibers have a temperature of 4 when pulled out from the coagulation bath.
It contained 5% by weight of solvent.
この未延伸１１１維を、第１水洗工程において、３０重
量％の溶媒を含む３０℃の水浴中を通して繊維中の溶媒
含有率を２５重量％に低下させた。次に、この繊維を第
１次水浴延伸工程において第１表に示す条件で２段延伸
した。In the first water washing step, the undrawn 111 fibers were passed through a 30° C. water bath containing 30% by weight of solvent to reduce the solvent content in the fibers to 25% by weight. Next, this fiber was drawn in two stages under the conditions shown in Table 1 in the first water bath drawing step.
第１表：第１次水浴延伸工程
このように第１次水浴延伸を行った繊維を、第２次水洗
工程において５０℃の水浴中で水洗して溶媒含有率を１
０重量％まで低下させた。引続き、第２次水浴延伸工程
において９０℃の水浴中で２．１倍に延伸した後、１２
０℃で乾燥し、次の乾熱延伸工程において３５０℃の熱
板上で１．７倍に延伸した。Table 1: First water bath drawing process The fibers subjected to the first water bath drawing are washed in a 50°C water bath in the second water washing process to reduce the solvent content to 1.
It was reduced to 0% by weight. Subsequently, in the second water bath stretching step, after stretching 2.1 times in a 90°C water bath,
It was dried at 0°C, and in the next dry heat stretching step, it was stretched 1.7 times on a hot plate at 350°C.
紡糸後の全延伸倍率は４．７倍であった。The total stretching ratio after spinning was 4.7 times.
この実験結果を後掲の第２表に示す。The results of this experiment are shown in Table 2 below.
比較例１
従来の方法によりポリメタフェニレンイソフタラミド繊
維を製造した。即ち、固有粘度［η］が１．３５のポリ
メタフェニレンイソフタラミドを用いて実施例１に準じ
て湿式紡糸し、凝固浴上りの未延伸繊維を６０℃の水浴
中で水洗して溶媒含有率を８重量％まで低下せしめた後
、９５℃の水浴中で２．４倍に延伸し、１３０℃で乾燥
後３５０℃の熱板上で１．７５倍に延伸した。この結果
を第２表に示す。Comparative Example 1 Polymetaphenylene isophthalamide fibers were produced by a conventional method. That is, wet spinning was performed according to Example 1 using polymetaphenylene isophthalamide having an intrinsic viscosity [η] of 1.35, and the undrawn fibers after the coagulation bath were washed with water in a 60° C. water bath to obtain solvent-containing fibers. After reducing the ratio to 8% by weight, it was stretched 2.4 times in a water bath at 95°C, dried at 130°C, and then stretched 1.75 times on a hot plate at 350°C. The results are shown in Table 2.
第２表 繊維の構造及び物性
第２表より明らかなごとく、従来のポリメタフェニレン
イソフタラミド繊維の強度は高々５．５９／ｄｅ程度で
あるのに対し、本発明の繊維は、７．２ｇ／ｄｅもの高
い破断強度を有し、従って、繊維の破断に至るまでの仕
事量を表わすシルクファクターも３９．４と、きわめて
高い値を示している。Table 2 Fiber structure and physical properties As is clear from Table 2, the strength of the conventional polymetaphenylene isophthalamide fiber is approximately 5.59/de at most, while the strength of the fiber of the present invention is 7.2g/de. It has a breaking strength as high as /de, and therefore its silk factor, which represents the amount of work required to break the fiber, is also extremely high at 39.4.
また、実施例１により得られた本発明の繊維を、バッグ
フィルター用フェルトの基布の基材として用いたところ
、従来の繊維を用いたものに比べ製品寿命が著しく延長
することが確認された。Furthermore, when the fiber of the present invention obtained in Example 1 was used as a base material for the base fabric of felt for bag filters, it was confirmed that the product life was significantly extended compared to those using conventional fibers. .
実施例２
特公昭４７−１０８６３号公報に記載の界面重合法によ
り固有粘度［η］ １．３５のポリメタフェニレンイ
ソフタラミド重合体を製造し、該重合体をＮ−メチル−
２−ピロリドンからなる溶媒に溶解しポリマー濃度２２
重量％の紡糸ドープを調製した。Example 2 A polymetaphenylene isophthalamide polymer having an intrinsic viscosity [η] of 1.35 was produced by the interfacial polymerization method described in Japanese Patent Publication No. 47-10863, and the polymer was mixed with N-methyl-
Polymer concentration 22 when dissolved in a solvent consisting of 2-pyrrolidone
% spinning dope was prepared.
このドープを特公昭４８−１７５５１号公報に記載の湿
式紡糸法に従って孔径０，０８ｍの紡糸孔を６０００有
する紡糸口金から塩化カルシウム濃度４３重量％。This dope was spun into a spinneret having 6,000 spinning holes with a diameter of 0.08 m according to the wet spinning method described in Japanese Patent Publication No. 17551/1983 to obtain a calcium chloride concentration of 43% by weight.
温度９５℃の塩化カルシウム水溶液からなる凝固浴中へ
湿式紡糸した。凝固浴上りの未延伸繊度の溶媒含有率は
４３重量％であった。この繊維を第１次水洗工程におい
て３０ｍ９％の溶媒を含む４０℃の水洗浴で水洗し！１
Ｉｆｆ中の溶媒含有率を２３重間％に低下させた。Wet spinning was carried out into a coagulation bath consisting of an aqueous calcium chloride solution at a temperature of 95°C. The solvent content of the undrawn fineness after the coagulation bath was 43% by weight. In the first washing process, this fiber was washed in a 40°C water washing bath containing 30ml and 9% solvent! 1
The solvent content in Iff was reduced to 23% by weight.
次に、この！ｌ維を第１次水浴延伸工程で第３表に示す
条件で２段延伸した。Next, this! The fibers were drawn in two stages under the conditions shown in Table 3 in the first water bath drawing step.
第３表：第１次水浴延伸工程
このように２段延伸したｌＩ維を常温の水中で洗浄して
繊維中の溶媒含有率を１２重量％以下まで低下させた後
、第２次水浴延伸工程に入り、９０℃の水浴中で２．２
倍に延伸した。延伸後の繊維はさらに９０℃の水中で洗
浄した後、１２０℃で乾燥し、引続ぎ、３５５℃の熱板
上で１．７倍に延伸した。紡糸後の全延伸倍率は４．９
倍であった。Table 3: First water bath drawing process After washing the II fibers thus drawn in two stages in water at room temperature to reduce the solvent content in the fibers to 12% by weight or less, the second water bath drawing process 2.2 in a 90℃ water bath.
Stretched twice. The stretched fibers were further washed in water at 90°C, dried at 120°C, and then stretched 1.7 times on a hot plate at 355°C. The total draw ratio after spinning is 4.9
It was double that.
この実験の結果は後掲の第５表に示す。The results of this experiment are shown in Table 5 below.
実施例３〜５．比較例３
次の第４表に示す条件以外は実施例２と同様にしてポリ
メタフェニレンイソフタラミド繊維を製造した。Examples 3-5. Comparative Example 3 A polymetaphenylene isophthalamide fiber was produced in the same manner as in Example 2 except for the conditions shown in Table 4 below.
これらの実験の結果は後掲の第５表に示す。The results of these experiments are shown in Table 5 below.
第４表：ｕ＆雑の製造条件
＊＊印は延伸浴中にＣａＣｊ２も含む
実施例６
純度９９．９５％のイソフタル酸クロライド（ＩＰＣ）
２１３．１８ Ｋｇを脱水したテトラヒドロフラン
（ＴＨＦ）（水分１００ＤＤＩｎ ）７５０文ニ溶解し
、これを撹拌磯、冷却コイル、冷却ジャケットを有する
容ｆｆ１２ＴｒＬ３の反応槽に入れ、毎分３００回転の
撹拌を行いながら一２２℃迄冷却した。一方、撹拌機。Table 4: u & miscellaneous manufacturing conditions ** indicates Example 6 where CaCj2 is also included in the drawing bath Isophthalic acid chloride (IPC) with a purity of 99.95%
213.18 kg was dissolved in 750 grams of dehydrated tetrahydrofuran (THF) (moisture 100 DDIn), and this was placed in a reaction tank with a capacity of ff12TrL3 equipped with a stirring rock, a cooling coil, and a cooling jacket, and the mixture was stirred at 300 revolutions per minute. It was cooled to -22°C. Meanwhile, a stirrer.
冷却コイル、冷却ジャケットを有する容０１ｍ３の溶解
槽で、純度９９．９３％のメタフェニレンジアミン（Ｍ
ＰＤＡ） １１３，５ｓＫｆｆを７５０ 、ＱのＴＨ
Ｆく水分率１１００ｐｐ ）に溶解し一２２℃迄冷却し
た。Metaphenylenediamine (M
PDA) 113,5sKff 750, Q TH
The solution was dissolved in F (moisture content: 1100 pp) and cooled to -22°C.
冷却されたＭＰＤＡのＴＨＦ溶液を４．．３Ｑ ／分の
添加速度で多数のノズル口より粒径０，１ａｍ以下の噴
霧状でＩＰＣのＴＨＥ溶液に２００分間で撹拌下に添加
すると白濁した乳化液が得られ、このときの反応槽の内
温は一１５℃であった。添加終了後約５分間撹拌を継続
した。4. Add the cooled THF solution of MPDA. ．． When it is added to the THE solution of IPC in the form of a spray with a particle size of 0.1 am or less at an addition rate of 3Q/min for 200 minutes with stirring from multiple nozzle ports, a cloudy emulsion is obtained, and the inside of the reaction tank at this time is The temperature was -15°C. Stirring was continued for approximately 5 minutes after the addition was complete.
高速撹拌曙を有する容ｆｆ１５ＴｒＬ３の反応槽に炭酸
ソーダ１５６ Ｋｇを水１７５０１に溶解した水溶液を
加え毎分１７００回転に撹拌後速かに前記の白濁した乳
化液を加え約５分間撹拌を継続した。反応系は数分後に
粘度が増大し、再び低下、白色の懸濁液が得られた。こ
れを濾過することにより白色粉末を得、濾別水洗後乾燥
し２４９．４Ｋｇ （収率９９．８％）のポリメタフェ
ニレンイソフタラミドの白色重合体が得られた。An aqueous solution of 156 kg of soda carbonate dissolved in 17501 of water was added to a reaction tank having a capacity of 15 TrL3 and equipped with high-speed stirring, and the mixture was stirred at 1,700 revolutions per minute.Then, the cloudy emulsion was quickly added, and stirring was continued for about 5 minutes. The viscosity of the reaction system increased after a few minutes and then decreased again, yielding a white suspension. This was filtered to obtain a white powder, which was separated by filtration, washed with water, and dried to obtain 249.4 kg (yield: 99.8%) of a white polymer of polymetaphenylene isophthalamide.
この重合体の固有粘度［η］は２．０であった。The intrinsic viscosity [η] of this polymer was 2.0.
この重合体は、高速液体クロマトグラフィで分子１分布
を測定すると、高分子吊物のピーク（Ａ）が著しく大と
なり９６．９％を占めるのに対し、低分子借物（Ｂビー
ク）は実質的にＯであり、またオリゴマー（Ｃビーク）
も著しく減少しており ３．１％であった。即ちこの重
合体は特に分子量分布がシャープになっていることが確
認された。When the molecule 1 distribution of this polymer was measured using high-performance liquid chromatography, the peak (A) of the polymer hanging material was extremely large and accounted for 96.9%, whereas the low molecular weight material (B peak) was substantially O, and also an oligomer (C beak)
There was also a significant decrease to 3.1%. That is, it was confirmed that this polymer had a particularly sharp molecular weight distribution.
この重合体をＮ−メチル−２−ピロリドン（ＮＭＰ）に
溶解して温度１８重量％の紡糸ドープとなし、実施例２
と同様に湿式紡糸した。This polymer was dissolved in N-methyl-2-pyrrolidone (NMP) to form a spinning dope at a temperature of 18% by weight. Example 2
Wet spinning was carried out in the same manner as above.
凝固浴上りの未延伸繊維は、４５重量％の溶媒を含んで
いた。この未延伸繊維を３０１良％の溶媒を含む３０℃
の水浴で水洗し、繊維中の溶媒含有率を２４重量％とじ
た。The undrawn fibers after the coagulation bath contained 45% by weight of solvent. This undrawn fiber was heated at 30°C containing 301% solvent.
The fibers were washed with water in a water bath to reduce the solvent content in the fibers to 24% by weight.
次に、この繊維を第１次水浴延伸工程において、次の条
件で２段延伸した。即ち、第１段で２０％の溶媒を含む
４５℃の水浴中で１．１倍に延伸し、続いて第２段で１
５重世％の溶媒を含む５０℃の水浴中で１．２倍に延伸
した。このように延伸した繊維は、次いで７０℃の水で
洗浄しｍ雑巾の溶媒含有率を１４１ｆｆｉ％まで低下さ
せた後、第２次水浴延伸工程において、次の条件で２段
延伸した。即ち、第１段で８０℃の水浴中で２．１倍に
延伸し、続いて第２段で９０℃の水浴中で１．１倍に延
伸した。Next, this fiber was drawn in two stages under the following conditions in the first water bath drawing step. That is, in the first stage, stretching is carried out to 1.1 times in a 45°C water bath containing 20% solvent, and then in the second stage, stretching is carried out by 1.1 times.
It was stretched 1.2 times in a water bath at 50° C. containing 5% solvent. The thus drawn fibers were then washed with water at 70° C. to reduce the solvent content of the m rag to 141 ffi%, and then subjected to two-step drawing under the following conditions in a second water bath drawing step. That is, in the first stage, the film was stretched 2.1 times in a water bath at 80°C, and then in the second stage, it was stretched 1.1 times in a water bath at 90°C.
かくして水浴延伸した繊維は、１３０℃で乾燥後、３５
５℃の熱板上で１．７０倍に乾熱処理した。After drying at 130°C, the fibers drawn in a water bath have a temperature of 35°C.
Dry heat treatment was performed on a hot plate at 5° C. to increase the size by 1.70 times.
この実験の結果を第５表に示す。The results of this experiment are shown in Table 5.
第５表：繊維の構造と物性
実施例７
純度９９．９５％イソフタル酸クロライド（ＩＰＣ）２
１３．１８ Ｋｇを脱水したテトラヒドロフラン（ＴＨ
Ｆ）（水分率１００１１１）Ｉｌｌ ） ７５０文に
溶解し、これを撹拌機、冷却コイル、冷却ジャケットを
有する容ｆｆ１２ＴｒＬ３の反応槽に入れ、毎分約３０
０回転の撹拌を行いながら一１０℃迄冷却した。他方の
撹拌機。Table 5: Fiber structure and physical properties Example 7 Purity 99.95% Isophthalic acid chloride (IPC) 2
13.18 Kg of dehydrated tetrahydrofuran (TH
F) (moisture content 100111)
The mixture was cooled to -10° C. while stirring at 0 rotations. the other stirrer.
冷却コイル、冷却ジャケットを有する容１１ｍ３の溶解
槽で純度９９．９３％メタフェニレンジアミン（ＭＰＯ
Ａ＞を７５０ Ｊｌの脱水したＴＨＦ（水分率１１００
ｐｐ ）に溶解し一１５℃ま迄冷却した。冷却されたＭ
ＰＤＡのＴＩ−（Ｆ溶液を８．５Ｎ／分の添加速度でノ
ズル口より粒径０，１＃ＩＩＩ＋以下の噴霧状でＩＰＣ
のＴＨＦ溶液中に１２０分間で撹拌下に添加した。Metaphenylenediamine (MPO
A> in 750 Jl of dehydrated THF (moisture content 1100
pp) and cooled to -15°C. cooled M
PDA's TI-(F solution was sprayed from the nozzle opening at a rate of 8.5 N/min with a particle size of 0.1#III+ or less, and then IPC was applied.
was added to the THF solution for 120 minutes while stirring.
このときの反応槽の内温は一４℃であった。添加終了後
約１０分後に４５０旦のアニリンを添加し撹拌し、白濁
した乳化液を得た。これとは別に高速撹拌機を有する容
量５ＴｒＬ３の反応槽に炭酸ソーダ１９５ Ｋｇを水１
７５０．Ｑに溶解した水溶液を加え、毎分１７００回転
に撹拌した。アニリン添加終了から１５分後の白濁した
乳化液を炭酸ソーダ水溶液中に加え、約５分間撹拌を継
続した。反応系は数秒後に粘度が増大し、再び低下白色
の熱温系が（９られた。濾過により白色粉末を濾別し、
水洗後乾燥し、２４９．２に’Ｊ （収率９９．７％）
の末端封鎖したポリメタフェニレンイソフタラミドの白
色重合体が得られた。この重合体の固有粘度［η１は１
．３２であった。また、重合体中の全末端基ｍの２６％
がアニリンにより封鎖されており、オリゴマー量は４．
１重量％であった。The internal temperature of the reaction tank at this time was -4°C. Approximately 10 minutes after the addition was completed, 450 degrees of aniline was added and stirred to obtain a cloudy emulsion. Separately, 195 kg of soda carbonate was added to 1 liter of water in a reaction tank with a capacity of 5 TrL3 equipped with a high-speed stirrer.
750. An aqueous solution dissolved in Q was added and stirred at 1700 revolutions per minute. Fifteen minutes after the completion of the addition of aniline, the cloudy emulsion was added to the aqueous sodium carbonate solution, and stirring was continued for about 5 minutes. The viscosity of the reaction system increased after a few seconds and decreased again to form a white hot system (9).The white powder was filtered off by filtration.
Washed with water and dried to 249.2'J (yield 99.7%)
A white polymer of end-capped polymetaphenylene isophthalamide was obtained. The intrinsic viscosity of this polymer [η1 is 1
．． It was 32. Also, 26% of the total terminal groups m in the polymer
is blocked by aniline, and the amount of oligomer is 4.
It was 1% by weight.
固有粘度［η］の平均値は１．３２であり、そのバラツ
キ（α）は０．０３であった。このことは固有粘度のバ
ラツキが非常に小さいことを示している。The average value of the intrinsic viscosity [η] was 1.32, and its variation (α) was 0.03. This shows that the variation in intrinsic viscosity is very small.
この重合体を用いて実施例２と同様にしてｍＭを製造し
た。Using this polymer, mM was produced in the same manner as in Example 2.
得られた繊維は、単糸繊度２ ｄｅ、複屈折率０．２０
、結晶化度５１％、結晶サイズ３９人、結晶配向度９
３％であり、破断強度は７．８ｇ／ ｄｅ、破断伸度は
２６％であって３９．８のシルクファクターを示した。The obtained fiber has a single yarn fineness of 2 de and a birefringence index of 0.20.
, crystallinity 51%, crystal size 39, crystal orientation 9
3%, the breaking strength was 7.8 g/de, the breaking elongation was 26%, and the silk factor was 39.8.
また、３００℃における収縮率は５．８％であった。Moreover, the shrinkage rate at 300°C was 5.8%.
この繊維を３００℃の乾熱下で２０時間保持したときの
強度維持率は９４％であった。When this fiber was kept under dry heat at 300° C. for 20 hours, the strength retention rate was 94%.
Claims (20)
フエニレンイソフタラミドからなりかつポリマー濃度０
．５ｇ／１００ｍｌの無水Ｎ−メチル−２−ピロリドン
溶液にて３０℃の温度で測定した固有粘度［η］ｆが０
．７〜２．５であるポリメタフエニレンイソフタラミド
系重合体からなる繊維であつて、０．１８〜０．２２の
複屈折率、４５〜５５％の結晶化度及び３５〜４５Åの
結晶サイズを有し、かつ破断時の強度が６．５ｇ／ｄｅ
以上、シルクファクターが３５以上であることを特徴と
する高強力ポリメタフエニレンイソフタラミド系繊維。(1) At least 95 mol% of the polymer repeating units consist of metaphenylene isophthalamide and the polymer concentration is 0.
．． The intrinsic viscosity [η]f measured at a temperature of 30°C with a 5g/100ml anhydrous N-methyl-2-pyrrolidone solution is 0.
．． 7 to 2.5, which has a birefringence of 0.18 to 0.22, a crystallinity of 45 to 55%, and crystals of 35 to 45 Å. size and strength at break of 6.5g/de
The above-mentioned high-strength polymetaphenylene isophthalamide fiber is characterized by having a silk factor of 35 or more.
第（１）項記載の高強力ポリメタフエニレンイソフタラ
ミド系繊維。(2) The high-strength polymetaphenylene isophthalamide fiber according to claim (1), which has a degree of crystal orientation of 90 to 95%.
求の範囲第（１）項記載の高強力ポリメタフェニレンイ
ソフタラミド系繊維。(3) The high-strength polymetaphenylene isophthalamide fiber according to claim (1), which has a strength at break of 7.0 g/de or more.
囲第（１）項記載の高強力ポリメタフエニレンイソフタ
ラミド系繊維。(4) The high-strength polymetaphenylene isophthalamide fiber according to claim (1), which has an elongation at break of 20 to 30%.
フエニレンイソフタラミドからなりかつポリマー濃度０
．５９／１００ｍｌの無水Ｎ−メチル−２−ピロリドン
溶液にて３０℃の温度で測定した固有粘度［η］が０．
７〜２．５であるポリメタフエニレンイソフタラミド系
重合体を、有機溶媒に溶解して紡糸ドープとなし、該紡
糸ドープを紡糸して得た未延伸繊維を第１次水洗工程に
賦して繊維中の有機溶媒含有率を１５重量％未満に調整
し、次いで第１次水浴延伸工程に賦して繊維中の有機溶
媒含有率が１５〜３０重量％の状態において少くとも１
段で１．１〜１．５倍に延伸し、引続き第２次水洗工程
に賦して繊維中の有機溶媒含有率を１５重量％未満に調
整した後、第２次水浴延伸工程に賦して少くとも１段に
て１．１倍以上に延伸し、次いで乾燥し、しかる後乾熱
延伸工程に賦して全延伸倍率が４．０〜７．０倍となる
ように延伸することを特徴とする高強力ポリメタフエニ
レンイソフタラミド系繊維の製造方法。(5) at least 95 mol% of the polymer repeating units consist of metaphenylene isophthalamide and the polymer concentration is 0;
．． The intrinsic viscosity [η] measured with 59/100 ml of anhydrous N-methyl-2-pyrrolidone solution at a temperature of 30°C is 0.
7 to 2.5 is dissolved in an organic solvent to form a spinning dope, and the undrawn fiber obtained by spinning the spinning dope is subjected to a first water washing step. The organic solvent content in the fiber is adjusted to less than 15% by weight, and then the organic solvent content in the fiber is adjusted to less than 15% by weight.
The fibers are stretched 1.1 to 1.5 times in a step, and then subjected to a second water washing step to adjust the organic solvent content in the fiber to less than 15% by weight, and then subjected to a second water bath drawing step. Stretch it to 1.1 times or more in at least one stage, then dry it, and then apply it to a dry heat stretching step and stretch it so that the total stretching ratio is 4.0 to 7.0 times. A method for producing characteristically high-strength polymetaphenylene isophthalamide fibers.
Ｎ′−ジメチルアセトアミド及びＮ，Ｎ′−ジメチルホ
ルムアミドからなる群から選ばれた少くとも１種の溶媒
である特許請求の範囲第（５）項記載の製造方法。(6) The organic solvent is N-methyl-2-pyrrolidone, N,
The manufacturing method according to claim (5), wherein at least one solvent is selected from the group consisting of N'-dimethylacetamide and N,N'-dimethylformamide.
繊維を紡糸ドープ中の有機溶媒と同じ有機溶媒を１０〜
４０重量％の濃度で含む少くとも１つの水浴にて水洗す
る特許請求の範囲第（５）項記載の製造方法。(7) In the first water washing process, the undrawn fibers immediately after wet spinning are treated with 10 to 10% of the same organic solvent as the organic solvent in the spinning dope.
The manufacturing method according to claim (5), wherein washing is carried out in at least one water bath containing a concentration of 40% by weight.
７０℃とする特許請求の範囲第（５）項又は第（７）項
記載の製造方法。(8) In the first water washing step, the temperature of the water washing bath is set to 20~20°C.
The manufacturing method according to claim (5) or (7), wherein the temperature is 70°C.
中に含まれる有機溶媒の一部を除去する特許請求の範囲
第（５）項記載の製造方法。(9) The manufacturing method according to claim (5), wherein in the first water bath stretching step, part of the organic solvent contained in the fiber is removed at the same time as the stretching.
５℃の温度で延伸する特許請求の範囲第（５）項記載の
製造方法。(10) In the first water bath drawing process, the fibers are
The manufacturing method according to claim (5), wherein the film is stretched at a temperature of 5°C.
延伸浴中に、紡糸ドープ中の有機溶媒と同じ有機溶媒を
３〜３０重量％の濃度で含有させる特許請求の範囲第（
５）項又は第（１０）項記載の製造方法。(11) In the first water bath drawing step, at least one drawing bath contains the same organic solvent as the organic solvent in the spinning dope at a concentration of 3 to 30% by weight (
The manufacturing method described in item 5) or item (10).
１０〜３０重量％の第１浴にて５０〜７０℃の温度で１
．１〜１．４倍に第１段延伸し、次いで有機溶媒濃度が
５〜１５重量％であってかつ第１浴の濃度よりも低い第
２浴にて７０〜９０℃の温度で第１次水浴延伸工程の全
延伸倍率が１．１〜１．５となる倍率で延伸する特許請
求の範囲第（５）項、第（１０）項又は第（１１）項記
載の製造方法。(12) In the first water bath stretching step, 1
．． The first stage is stretched to 1 to 1.4 times, and then the first stage is stretched at a temperature of 70 to 90°C in a second bath with an organic solvent concentration of 5 to 15% by weight and lower than that of the first bath. The manufacturing method according to claim 5, claim 10, or claim 11, wherein the total stretching ratio in the water bath stretching step is 1.1 to 1.5.
の水浴中を通して繊維中の有機溶媒含有率を１５重量％
未満に調整する特許請求の範囲第（５）項記載の製造方
法。(13) In the second water washing step, the fibers are passed through at least one water bath to reduce the organic solvent content in the fibers to 15% by weight.
The manufacturing method according to claim (5), wherein the manufacturing method is adjusted to less than or equal to
℃の温度で水洗する特許請求の範囲第（５）項又は第（
１３）項記載の製造方法。(14) In the second water washing process, the fibers are
Claims (5) or (5) washing with water at a temperature of °C.
13) The manufacturing method described in section 13).
１段で１．５〜３．０倍に延伸する特許請求の範囲第（
５）項記載の製造方法。(15) In the second water bath drawing step, the fibers are drawn 1.5 to 3.0 times in at least one stage.
The manufacturing method described in section 5).
維中に残留する有機溶媒の少くとも一部を除去する特許
請求の範囲第（５）項又は第（１５）項記載の製造方法
。(16) The manufacturing method according to claim (5) or (15), wherein in the second water bath stretching step, at least a part of the organic solvent remaining in the fiber is removed at the same time as the stretching.
００℃の温度で延伸する特許請求の範囲第（５）項、第
（１５）項又は第（１６）項記載の製造方法。(17) In the second water bath drawing process, the fibers are
The manufacturing method according to claim (5), (15) or (16), wherein the film is stretched at a temperature of 00°C.
℃の温度で延伸する特許請求の範囲第（５）項記載の製
造方法。(18) In the dry heat drawing process, the fibers are
The manufacturing method according to claim (5), which involves stretching at a temperature of .degree.
倍に延伸する特許請求の範囲第（５）項又は第（１８）
項記載の製造方法。(19) In the dry heat drawing process, the fiber is
Claim (5) or (18) stretching to double
Manufacturing method described in section.
回水洗する特許請求の範囲第（１５）項記載の製造方法
。(20) After the second water bath drawing process, the fibers are
The manufacturing method according to claim (15), which comprises washing twice with water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27693485 | 1985-12-11 | ||
| JP60-276934 | 1985-12-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62231014A true JPS62231014A (en) | 1987-10-09 |
| JPH0532490B2 JPH0532490B2 (en) | 1993-05-17 |
Family
ID=17576441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61293528A Granted JPS62231014A (en) | 1985-12-11 | 1986-12-11 | High-strength polymetaphenylene isophthalamide yarn and production thereof |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4842796A (en) |
| EP (1) | EP0226137B1 (en) |
| JP (1) | JPS62231014A (en) |
| CA (1) | CA1282923C (en) |
| DE (1) | DE3682572D1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011042921A (en) * | 2005-07-06 | 2011-03-03 | Kolon Industries Inc | Wholly aromatic polyamide filament |
| JP2019081968A (en) * | 2017-10-30 | 2019-05-30 | 帝人株式会社 | Dyed meta-type wholly aromatic polyamide fiber, spun yarn, fabric, and textile product |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5023035A (en) * | 1989-02-21 | 1991-06-11 | E. I. Du Pont De Nemours And Company | Cyclic tensioning of never-dried yarns |
| EP0511456A1 (en) * | 1991-04-30 | 1992-11-04 | The Procter & Gamble Company | Liquid detergents with aromatic borate ester to inhibit proteolytic enzyme |
| JP2600066B2 (en) * | 1995-03-29 | 1997-04-16 | 財団法人工業技術研究院 | Method for preparing soluble wholly aromatic polyamide fibers |
| US5667743A (en) * | 1996-05-21 | 1997-09-16 | E. I. Du Pont De Nemours And Company | Wet spinning process for aramid polymer containing salts |
| US6485136B1 (en) * | 1998-06-26 | 2002-11-26 | Canon Kabushiki Kaisha | Absorber and container for ink jet recording liquid using such absorber |
| US20050093198A1 (en) * | 2003-10-31 | 2005-05-05 | Rodini David J. | Wet spinning process for aramid polymer containing salts |
| CN103897849A (en) * | 2012-12-26 | 2014-07-02 | 青岛锦涟鑫商贸有限公司 | Detergent for fiber fabric |
| CN103233292B (en) * | 2013-04-28 | 2016-08-10 | 圣欧芳纶（江苏）股份有限公司 | A kind of preparation method of meta-aramid fibers |
| US20220380939A1 (en) | 2019-10-07 | 2022-12-01 | Teijin Limited | Process for the manufacture of a fiber comprising meta-aramid |
| CN110804767B (en) * | 2019-11-04 | 2022-04-26 | 赣州龙邦材料科技有限公司 | Aramid 1313 fiber and preparation method and application thereof |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL108880C (en) * | 1957-02-28 | |||
| US3094511A (en) * | 1958-11-17 | 1963-06-18 | Du Pont | Wholly aromatic polyamides |
| US3079219A (en) * | 1960-12-06 | 1963-02-26 | Du Pont | Process for wet spinning aromatic polyamides |
| US3414645A (en) * | 1964-06-19 | 1968-12-03 | Monsanto Co | Process for spinning wholly aromatic polyamide fibers |
| US3287324A (en) * | 1965-05-07 | 1966-11-22 | Du Pont | Poly-meta-phenylene isophthalamides |
| FR1482822A (en) * | 1965-06-19 | 1967-06-02 | Monsanto Co | Process for the spinning of heat-resistant fibers and products obtained by this process |
| US3300450A (en) * | 1966-04-12 | 1967-01-24 | Du Pont | Stabilized aromatic polyamide filaments |
| US3560137A (en) * | 1967-08-15 | 1971-02-02 | Du Pont | Wholly aromatic polyamides of increased hydrolytic durability and solvent resistance |
| US3642706A (en) * | 1970-03-03 | 1972-02-15 | Monsanto Co | Process for spinning wholly aromatic polyamide filaments |
| DE2037254A1 (en) * | 1970-07-28 | 1972-02-03 | Farbwerke Hoechst AG, vorm. Meister Lucius & Brüning, 6000 Frankfurt | Process for the production of threads from high-melting polyamides |
| US3869429A (en) * | 1971-08-17 | 1975-03-04 | Du Pont | High strength polyamide fibers and films |
| US4073837A (en) * | 1972-05-18 | 1978-02-14 | Teitin Limited | Process for producing wholly aromatic polyamide fibers |
| JPS55122011A (en) * | 1979-03-13 | 1980-09-19 | Asahi Chem Ind Co Ltd | Poly-p-phenylene terephthalamide fiber having high young's modulus and its preparation |
| US4342715A (en) * | 1980-10-29 | 1982-08-03 | Teijin Limited | Process for preparing wholly aromatic polyamide shaped articles |
-
1986
- 1986-12-02 CA CA000524384A patent/CA1282923C/en not_active Expired - Lifetime
- 1986-12-04 EP EP86116873A patent/EP0226137B1/en not_active Expired
- 1986-12-04 DE DE8686116873T patent/DE3682572D1/en not_active Expired - Lifetime
- 1986-12-11 JP JP61293528A patent/JPS62231014A/en active Granted
-
1987
- 1987-12-11 US US07/133,175 patent/US4842796A/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011042921A (en) * | 2005-07-06 | 2011-03-03 | Kolon Industries Inc | Wholly aromatic polyamide filament |
| JP2019081968A (en) * | 2017-10-30 | 2019-05-30 | 帝人株式会社 | Dyed meta-type wholly aromatic polyamide fiber, spun yarn, fabric, and textile product |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0226137A2 (en) | 1987-06-24 |
| JPH0532490B2 (en) | 1993-05-17 |
| CA1282923C (en) | 1991-04-16 |
| DE3682572D1 (en) | 1992-01-02 |
| EP0226137B1 (en) | 1991-11-21 |
| EP0226137A3 (en) | 1988-01-27 |
| US4842796A (en) | 1989-06-27 |
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